The present invention relates to a method for shifting the absorption peak wavelength of an infrared radiation absorbing glass. More particularly, the invention relates to a method for shifting the absorption peak wavelength in the wavelength range 900-1200 nm of an infrared radiation absorbing glass from less than 1100 nm to 1100 nm or longer without changing a visible light transmission of the glass.
From the standpoint in reduction of the load of air conditioning in automobiles, a glass having infrared absorbing power has recently been proposed as window panes of automobiles.
For example, greenish blue-tinted glass having a relatively high Fe2O3 content to exhibit improved infrared absorbing power has been developed for use in automobiles. A typical example of such a greenish blue-tinted infrared absorbing glass has a composition comprising, in % by weight: 71% SiO2, 1.5% Al2O3, 4% MgO, 8.6 t % CaO, 13.5% Na2O, 0.7% K2O, 0.55% total iron oxides in terms of Fe2O3, and 0.17 FeO in terms of Fe2O3. The glass having this composition with a thickness of 4 mm has a visible light transmission of 78% as measured with the CIE standard illuminant A and a solar energy transmission of 54%.
Glass having a bronze tint, on the other hand, contains Fe2O3 in an amount smaller than that in the greenish blue-tinted glass so as to have fair infrared absorbing power while maintaining visible light transmission. A typical example of infrared radiation absorbing glass having a bronze tint has a composition of, in % by weight: 72% of SiO2, 1.5% Al2O3, 4% MgO, 8% CaO, 13.5% Na2O, 0.7% K2O, 0.24% total iron oxides in terms of Fe2O3, 0.054% of FeO in terms of Fe2O3, 0.001% CoO, and 0.001 wt % of Se. The glass having this composition with a thickness of 4 mm has a visible light transmission of 78% as measured with the CIE standard illuminant A and a solar energy transmission of 70%.
In the above-described conventional infrared radiation absorbing glass, its infrared absorbing power is imparted by Fe2+ (FeO). However, if the FeO concentration in a greenish blue-tinted glass is increased in order to obtain higher infrared absorbing power, the absorption of FeO in the visible region increases, and as a result, there is particularly a problem that the visible light transmission required of windowpanes of vehicles cannot be obtained. In a glass which forms a color utilizing absorption of Se in the visible region, such as bronze type glass, there is the problem that greater restriction is imposed on the FeO concentration, and a high infrared absorbing power is not obtained.
The present invention has been made in view of the above-described problems involved in the prior art.
An object of the present invention is to provide a method for producing a glass having a high infrared absorbing power and a high visible light transmission.
According to one embodiment of the present invention, there is provided a method for shifting the absorption peak wavelength in the wavelength range 900-1600 nm of an infrared radiation absorbing glass from less than 1100 nm to 1100 nm or longer without substantially changing the tint of the glass, comprising the step of irradiating the glass which comprises, in % by weight:
65 to 80% SiO2,
0 to 5% Al2O3,
0 to 10% MgO,
5 to 15% CaO,
10 to 18% Na2O,
0 to 5% K2O,
5 to 15% MgO+CaO,
10 to 20% Na2O+K2O, and
0 to 5% B2O3;
0.02% or more total iron oxide (T-Fe2O3) in terms of Fe2O3,
0 to 2.0% CeO2,
0 to 1.0% TiO2,
0 to 0.005% CoO, and
0 to 0.005% Se,
with ultraviolet light of 400 nm or shorter at an energy density of 1.0xc3x97106 J/m2/hr pr more to increase the content of FeO in the irradiated glass by reducing Fe(III) to Fe(II), the ultraviolet light irradiated glass thereby comprising 0.02 wt. % or more FeO in terms of Fe2O3.
Preferably, the infrared radiation absorbing glass comprises, in % by weight:
0.05% or more T-Fe2O3 in terms of Fe2O3.
Preferably, the infrared radiation absorbing glass comprises, in % by weight:
0.05 to 1.0% T-Fe2O3 in terms of Fe2O3, and
0.02 to 0.5% FeO in terms of Fe2O3.
Preferably, the infrared radiation absorbing glass comprises, in % by weight:
0.02 to 0.6% T-Fe2O3 in terms of Fe2O3;
0.02 to 0.3 FeO in terms of Fe2O3;
0.2 to 2.0% CeO2; and
0.0005 to 0.005% Se,
wherein the relationship between the transmission at 1,050 nm (T1050) and the transmission at 1,200 nm (T1200) is T1050 greater than T1200.
According to another embodiment of the present invention, there is provided a method for shifting the absorption peak wavelength in the wavelength range 900-1600 nm of an infrared radiation absorbing glass from less than 1100 nm to 1100 nm or longer without substantially changing the tint of the glass, comprising the step of irradiating the glass which comprises, in % by weight:
65 to 80% SiO2,
0 to 5% Al2O3,
0 to 10% MgO,
5 to 15% CaO,
10 to 18% Na2O,
0 to 5% K2O,
5 to 15% MgO+CaO,
10 to 20% Na2O+K20, and
0 to 5% B2O3;
0.05% or more total iron oxide (T-Fe2O3) in terms of Fe2O3,
0.5 to 3% total of one or more components selected from CeO2, Sb2O3, As2O3, SnO and Cu2O,
0 to 1.0% TiO2,
0 to 0.005% CoO, and
0 to 0.005% Se,
with ultraviolet light of 400 nm or shorter at an energy density of 1.0xc3x97106 J/m2/hr or more to increase the content of FeO in the irradiated glass by reducing Fe(III) to Fe(II), the ultraviolet light irradiated glass thereby comprising 0.02 wt. % or more FeO in terms of Fe2O3.
The infrared radiation absorbing glasses according to the present invention preferably have a visible light transmission of 70% or more as measured with the CIE standard illuminant A and a total solar energy transmission of less than 70% as measured in the wavelength region of from 300 to 2,100 nm, when the thickness of the glass is 4 mm.
It is also preferred that the infrared radiation absorbing glasses according to the present invention have a dominant wavelength of 574 to 580 nm as measured with the CIE standard illuminant C and a total sunlight UV transmission of less than 12% as measured in a wavelength region of 297.5 to 377.5 nm according to ISO 9050, when the thickness of the glasses is 4 mm.
It is further preferred that the infrared radiation absorbing glasses according to the present invention have an ultraviolet transmission of less than 34% at a wavelength of 370 nm, when the thickness of the glasses is 4 mm.
The reasons for limitation of the glass compositions of the infrared radiation absorbing glass used in the method according to the present invention are explained below. Hereinafter, unless otherwise indicated, all the percents are by weight.
Iron oxide is present in glass in the form of Fe2O3 (Fe3+) and FeO (Fe2+). Fe2O3is a component serving to increase an infrared absorbing power, while FeO is a component serving to increase an ultraviolet absorbing power together with CeO2 and TiO2.
In general soda lime silica glass composition used as window glass of buildings and vehicles, Fe2+ shows its absorption peak at about 1,050 nm and also has an absorption in the visible light region of from 400 to 780 nm. Therefore, if the FeO content is increased, the infrared absorbing power is increased, but a visible light transmission is simultaneously decreased. The gist of the present invention resides in shifting the absorption peak wavelength of Fe2+ to a longer wavelength side to minimize the decrease in visible light transmission, thereby achieving both a high infrared absorbing power and a high visible light transmission at a time.
The absorption peak wavelength of Fe2+ is shifted to the longer wavelength side by irradiating the glass with ultraviolet light at around room temperature.
The inventors of the present invention have found that ultraviolet irradiation of appropriate glass containing Fe2O3 under appropriate conditions easily results in formation of Fe2+ having its absorption peak wavelength shifted to the longer wavelength side. Specifically, when glass containing a component acting as a photo-reducing agent, such as Ce3+, and Fe3+ is irradiated with UV at around room temperature, Fe2+ is formed through the reaction: Fe3++exe2x88x92xe2x86x92Fe2+. While the absorption peak of Fe2+in a general soda lime silica glass composition for windows is at about 1050 nm, that of the Fe2+ newly formed in glass on ultraviolet irradiation is shifted to the longer wavelength side, i.e., at about 1,200 nm or even more. This is because the thus formed Fe2+ is surrounded by a distorted structure. The absorption peak of glass in an infrared region after ultraviolet irradiation is determined by the overlap between the absorption of the originally present Fe2+ before irradiation and the absorption of the newly formed Fe2+ after irradiation, and is usually at a wavelength of from 1,100 to 1,250 nm, although varying depending on the glass composition, ultraviolet irradiation conditions, and the like.
Ultraviolet irradiation is conducted using ultraviolet light of 400 nm or shorter at an energy density of 1.0xc3x97106 J/m2/hr or more.
Irradiation energy (a product of an irradiation energy density per unit time per unit area and an irradiation time) is preferably 7.0xc3x97107 to 5.0xc3x97108 J/m2.
The shift of the absorption peak wavelength to the longer wavelength side can be evaluated by comparing the transmissions at the peak wavelength. In the present invention, the shift is expressed in terms of change in the wavelength at which the transmission has the minimum value in the range of from 900 to 1,600 nm (xcexp) or in terms of the comparison between the transmission at 1,050 nm (T1050) and the transmission at 1,200 nm (T1200). xcexp is obtained, for example, as the minimum value of a transmission curve obtained by subjecting general smoothing treatment to the transmission data measured for each 2 nm or smaller.
If the total iron oxide (T-Fe2O3) content is too small, the infrared absorption power and ultraviolet absorbing power are decreased. If it is too, large, the visible light transmission is decreased. Accordingly, the T-Fe2O3 content should be 0.02% or more, and preferably from 0.05 to 1.0%. In the glass composition containing Se, for the formation of a bronze tint, the T-Fe2O3 content is preferably 0.2 to 0.6%.
If the FeO content is too small, the infrared absorbing power is decreased, and if it is too large, a visible light transmission is decreased. Accordingly, the FeO content should be 0.02% or more, and preferably from 0.02 to 0.5%, in terms of Fe2O3. In the glass composition containing Se, for the formation of a bronze tint, the FeO content preferably is from 0.02 to 0.3%.
CeO2 is a component for enhancing ultraviolet absorption. It exists in glass in the form of Ce3+ or Ce4+. While Ce3+ shows weak absorption in the visible region and is more effective for UV absorption, it is an important component for its function as a photo-reducing agent in the present invention. Specifically, when glass containing Ce3+ is irradiated with ultraviolet light at around room temperature, Ce3+ acts as a photo-reducing agent, emitting an electron through the reaction: Ce3+xe2x86x92Ce4++exe2x88x92. The thus emitted electron functions in the reaction: Fe3++exe2x88x92xe2x86x92Fe2+, in which Fe2O3 is reduced to form FeO. As described above, the thus formed FeO has its infrared absorption peak at a wavelength of about 1,200 nm or longer, which is a wavelength shifted to the long wavelength side as compared with about 1,050 nm of the FeO formed by a melt method in the production of general soda lime silica glass for windows. As a result, the glass after ultraviolet irradiation has an absorption peak in the infrared region at a wavelength of from about 1,100 to 1,250 nm, and thus can exhibit improved infrared absorbing power while minimizing the decrease in visible light transmission. The CeO2 content should be 2.0% or less. If the CeO2 content is too large, the absorption in the short wavelength side in the visible region is so large that the resulting glass assumes a yellow tint. To ensure a satisfactory function as a photo-reducing agent and to obtain an ultraviolet absorbing power, the CeO2 content is preferably 0. 05 to 2.0%, more preferably 0.2 to 2.0%, and most preferably more than 0.5 to 2.0%.
SiO2 is a main component for forming a network structure of the glass. If the SiO2 content is less than 65%, the glass has a reduced durability. If it exceeds 80%, it is difficult to melt the glass composition.
Al2O3 serves to improve durability of glass. If the Al2O3 content exceeds 5%, it is difficult to melt the glass of the composition. A preferred Al2O3 content is 0.1 to 2%.
MgO and CaO both serve to improve durability of glass and also to control the liquidus temperature and viscosity in forming the glass. If the MgO content exceeds 10%, the liquidus temperature rises. If the CaO content is less than 5% or higher than 15%, the liquidus temperature rises. If the total content of MgO and CaO is less than 5%, the resulting glass has reduced durability. If the total content exceeds 15%, the liquidus temperature rises.
Na2O and K2O are used as a glass melting accelerator. If the Na2O content is less than 10%, or if the total content of Na2O and K2O is less than 10%, the effect of melting acceleration is weak. If Na2O content exceeds 18%, or if the total content of Na2O and K2O exceeds 20%, durability of glass is decreased. K2O is effective to enhance the pink color development of Se and simultaneously to increase the ultraviolet absorbing power. It is unfavorable for the K2O content to exceed 5% because it is more expensive than Na2O.
While B2O3 is a component used for the improvement of durability of glass and also as a melting aid, it also functions to enhance ultraviolet absorption. If the B2O3 content exceeds 5.0%, decrease in the light transmission in the ultraviolet region is also extended to the visible region, and the glass tends to assume a yellow tint. Moreover, disadvantages occur due to vaporization of B2O3 in forming glass. Accordingly, the upper limit of the B2O3 content should be 5.0%.
TiO2 is a component for increasing ultraviolet absorbing power through the mutual action especially with FeO. If the TiO2 content exceeds 1.0%, the glass assumes a yellow tint.
CoO is a component which develops a bronze color in the presence of Se. If the CoO content exceeds 0.005%, the visible light transmission is reduced.
Se develops a pink tint to thereby provide a bronze tint coupled with CoO which has a complementary color to the pink tint. If the Se content is less than 0.0005%, a desired color cannot be obtained. If it exceeds 0.005%, the visible light transmission is reduced.
Sb2O3, As2O3, SnO, and Cu2O function as a photo-reducing agent similar to CeO2 or serve to accelerate the reducing action of CeO2. If the total content of any one or more of these 5 components (inclusive of CeO2) is less than 0.05%, the photo-reducing effect is small. The upper limit of the total content of the 5 components is 3% because of their expensiveness.
So long as the effect as aimed at in each embodiment of the present invention is not impaired, the glass composition according to the present invention may further contain one or more of ZnO, Bi2O3, NiO, MnO, and MoO3 in a total amount of up to 1%; one or more of F, Cl, and Br in a total amount of up to 1%; and up to 1% of S in terms of SO3.
The glass composition according to the present invention does not substantially contain V2O5, except that V2O5 is contained as an unavoidable impurity resulted from starting materials of glass.
The present invention is described in greater detail below by reference to the following Examples, but it should be understood that the invention is not construed as being limited thereto.